CN101250028A - Glass sheet with antireflection film and laminated glass for windows - Google Patents
Glass sheet with antireflection film and laminated glass for windows Download PDFInfo
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- CN101250028A CN101250028A CNA200810081054XA CN200810081054A CN101250028A CN 101250028 A CN101250028 A CN 101250028A CN A200810081054X A CNA200810081054X A CN A200810081054XA CN 200810081054 A CN200810081054 A CN 200810081054A CN 101250028 A CN101250028 A CN 101250028A
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- China
- Prior art keywords
- film
- antireflective coating
- sheet glass
- glass
- nanometer
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
Abstract
A glass substrate with antireflection film is provided, which has sufficient antireflection performance for obliquely incident light, high visible light transmittance, sufficient abrasion resistance and good transmittance for electromagnetic waves, which is sufficiently durable against heat treatment in the production process, to which treatment after film-forming is applicable, and which has smaller number of films and thus is producible at low cost. A glass sheet with antireflection film, comprising a glass sheet and an antireflection film composed of at least two layers and provided on a surface of the glass sheet, wherein the antireflection film comprises a film (a) made of a high refractive index material having a refractive index of from 1.8 to 2.6 and an extinction coefficient of from 0.01 to 0.65 in a wavelength region of from 380 to 780 nm, and a film (b) made of a low refractive index material having a refractive index of at most 1.56 in a wavelength region of from 380 to 780 nm, and wherein the film (b) is positioned at an outermost surface of the antireflection film and the antireflection film has a sheet resistance of at least 1 kOmega/-.
Description
Technical field
The laminated glass that the present invention relates to have the sheet glass of antireflective coating and be used for window.
Background technology
In some cases, glass baseplate needs the antireflective function.For example, the glass baseplate that is used as windshield (front glass) need have the antireflective function to the visible light of oblique incidence, with the light formation projection of inhibition from for example dashboard, thus the sharpness of raising driver's seat.
For example, patent documentation 1 has been described a kind of glass with antireflective coating that is used for the carrier vehicle window, as the glass with antireflective coating that can satisfy this function, described film is included in the film that forms according to following order on the base material: the main extinction film with pre-determined thickness that is formed by nitride; And have the predetermined specific refractory power and an oxide film of thickness.This antireflective coating has enough low specific refractory power and sufficiently high transmission of visible light to the incident light that tilts, have enough wear resistancies, film is very thin, can be with the low cost manufacturing, and the thermal treatment in the production process (for example being used for the thermal treatment of bending process) had enough tolerances.
In recent years, except above-mentioned performance, also exist and to have radioparent situation to hertzian wave.For example, people are in order to provide antenna on base material, and the window glass that is used for windshield recently need have transmissivity to hertzian wave.
But, because the glass with antireflective coating that this carrier vehicle window of describing in the patent documentation 1 is adopted has low resistance, and the meeting shielding electromagnetic wave, it is to electromagnetic transmissivity deficiency.
In order to address this problem, patent documentation 2 has proposed a kind of base material with antireflective coating, it has high visible light transmissivity, antiradar reflectivity and high sheet resistance (promptly hertzian wave being had good transmissivity), even can not crack heat treated the time being subjected to yet, base material with antireflective coating comprises transparent substrate and antireflective coating, and described antireflective coating comprises from the side of described transparent substrate with the stacked coating of following order: the total coated membrane of being made by high-index material of total even level; A coated membrane of making by low-index material, wherein at least one coated membrane of being made by high-index material is following film: the unitary film of titanium oxynitrides (a), the stacked film (b) that comprises titanium oxide layer and zirconia layer perhaps comprises the stacked film (c) of titanium oxynitrides layer and zirconia layer.
Patent documentation 1:WO2000/33110
Patent documentation 2:WO2006/80502
But the problem of the base material with antireflective coating described in the above-identified patent document 2 is that it comprises a large amount of stacked layers, and its manufacturing cost is very high.
In order to address these problems, a target of the present invention provides a kind of base material with antireflective coating, it has and the patent documentation 2 described suitable superperformances of base material with antireflective coating, and has the overlapped layers of lesser amt, has good throughput.
That is to say, a target of the present invention provides the sheet glass with antireflective coating, and it has enough low reflectivity to oblique incidence light, has high visible light transmissivity, enough wear resistancies, hertzian wave is had good transmissivity, the thermal treatment in the production process is had enough tolerances, can carry out film forming processing afterwards it, can reduce the quantity of overlapped layers (film), to reduce the thickness of whole film, have splendid throughput, can be with the low cost manufacturing.In addition, another target of the present invention provides the laminated glass that is used for window, and it uses above-mentioned sheet glass with antireflective coating, has enough low reflectivity, high visible light transmissivity, enough wear resistancies and good Electromgnetically-transparent.
Summary of the invention
The present invention includes following content (1) to (12).
(1) a kind of sheet glass with antireflective coating, it comprises sheet glass and antireflective coating, described antireflective coating is made up of at least two layers, be provided on the surface of described sheet glass, described antireflective coating comprises film (a) and film (b), described film (a) is made by high-index material, the specific refractory power of described high-index material in the 380-780 nanometer wavelength range is 1.8-2.6, optical extinction coefficient is 0.01-0.65, described film (b) is made by low-index material, the specific refractory power of described low-index material in the 380-780 nanometer wavelength range is up to 1.56, described film (b) is positioned at the outermost surface of described antireflective coating, and the sheet resistance of described antireflective coating is at least 1k Ω/.
(2) as mentioned (1) described sheet glass with antireflective coating, wherein, the geometrical film thickness degree of described film (a) is the 2-80 nanometer, the geometrical film thickness degree of described film (b) is the 80-300 nanometer.
(3) as mentioned (1) or (2) described sheet glass with antireflective coating, wherein, the main ingredient of described high-index material is metal oxide (A), it comprise be selected from following at least a: Co, Al, Si, Zn, Zr and V.
(4) as mentioned (3) described sheet glass with antireflective coating, wherein, described metal oxide (A) be selected from following at least a: the Co-Al oxide compound, the Co-Zn-Al oxide compound, Co-Al-Si oxide compound, Co-Zn-Si oxide compound, Co-Si oxide compound and Zr-Si-V oxide compound.
(5) as mentioned (3) or (4) described sheet glass with antireflective coating, wherein, described metal oxide (A) comprises Co and Al, and the atomic ratio of Al and Co (Al/Co) is 0.5-15.
(6) as mentioned (3) to (5) described sheet glass with antireflective coating, wherein, described metal oxide (A)
Be CoAl
XO
Y(0.5≤X≤15,1.75≤Y≤24).
(7) as mentioned (1) to (6) described sheet glass with antireflective coating, wherein, described low-index material is a silicon oxide.
(8) be used for the laminated glass of window, it comprises first sheet glass, second sheet glass with antireflective coating of forming by at least two layers, and the middle layer between described first sheet glass and second sheet glass, described second sheet glass is arranged on the indoor, described second sheet glass has antireflective coating, and this second sheet glass is each defined sheet glass with antireflective coating in (1) to (7) as mentioned, and the outermost surface of described antireflective coating is arranged on the indoor.
(9) as mentioned (8) described laminated glass that is used for window, its transmission of visible light (Tv) under 0 ° of input angle condition is at least 70%.
(10) as mentioned (8) or (9) described laminated glass that is used for window, wherein, under 60 ° of input angle conditions, visible light is 11% to the maximum at the reflectivity (Rv) on the film surface of described antireflective coating.
(11) as mentioned (8) to (10) described laminated glass that is used for window, wherein, under the condition of 0 ° of input angle, visible light is 8% to the maximum at the reflectivity (Rv) on the film surface of antireflective coating.
(12) a kind of preparation (1) to (7) described method with sheet glass of antireflective coating as mentioned, wherein, described at least film (a) forms by sputter.
According to the present invention, a kind of sheet glass with antireflective coating might be provided, it has enough low reflectivity to oblique incidence light, have high visible light transmissivity, enough wear resistancies and good Electromgnetically-transparent have enough tolerances to the thermal treatment in the production process, can apply film forming processing afterwards to it, can reduce the quantity of film and reduce the integral thickness of film, have splendid throughput, can be with the low cost manufacturing.
To describe the present invention in detail below.
Description of drawings
In the accompanying drawings:
Fig. 1 is the CoAl of each embodiment
xO
yThe wavelength dispersion of the specific refractory power of film (wavelength dispersion) figure.
Fig. 2 is the CoAl of each embodiment
xO
yThe wavelength dispersion figure of the optical extinction coefficient of film.
Fig. 3 is the SiO of embodiment
2The wavelength dispersion figure of the specific refractory power of film.
Embodiment
The invention provides sheet glass with antireflective coating, it comprises sheet glass and antireflective coating, described antireflective coating is made up of at least two layers, be provided on the surface of described sheet glass, described antireflective coating comprises film (a) and film (b), described film (a) is made by high-index material, the specific refractory power of described high-index material in the 380-780 nanometer wavelength range is 1.8-2.6, optical extinction coefficient is 0.01-0.65, described film (b) is made by low-index material, the specific refractory power of described low-index material in the 380-780 nanometer wavelength range is up to 1.56, described film (b) is positioned at the outermost surface of described antireflective coating, and the sheet resistance of described antireflective coating is at least 1k Ω/.Described antireflective coating has the multimembrane structure.Also this sheet glass with antireflective coating is called " anti reflection glass of the present invention " below.
Sheet glass of the present invention is not subjected to concrete restriction, as long as its sheet material for being made by glass.For example, can be float glass (by the glass of float glass process manufacturing) or colored antisolar glass etc.The sheet glass that they are preferably transparent.In addition, the thickness of sheet glass of the present invention is not particularly limited, but for example used thickness is about the sheet glass of 1.5-3.0 millimeter.This glass baseplate can have smooth shape or crooked shape.Because many vehicles (the particularly vehicle window of automobile) have curved part, so the shape of described sheet glass can be crooked.
In anti reflection glass of the present invention, sheet resistance preferably is at least 1k Ω/, more preferably is at least 5k Ω/.If described sheet resistance is at least 1k Ω/, then can obtain enough to electromagnetic transmissivity, this means that for example the signal receiving performance of TV and broadcasting is no problem.Therefore, as long as material allows, the upper limit of sheet resistance there is not particular restriction.
In recent years, because the development of digital television broadcasting aspect widespread use, people need use the high frequency of UHF wavestrip or higher frequency, receive broadcast wave with high gain of antenna.For this purpose, for example in automobile, except the rear portion or top that antenna are arranged on automobile, also it is arranged on the windshield glass place.In addition,, need have high transmissivity, therefore, need the sheet resistance of windshield glass to be at least 10M Ω/ and (preferably be at least 40M Ω/) hertzian wave in order to receive the broadcast wave of UHF wavestrip or higher frequency.Sheet resistance with sheet glass of antireflective coating of the present invention is at least 1G Ω/ usually, and is same as shown in the embodiment.Therefore, not only can receive conventional TV or broadcast wave, and the broadcast wave of reception UHF wave band or higher frequency is also no problem.
In the present invention, sheet resistance is represented the sheet resistance by dicyclo method mensuration.
In anti reflection glass of the present invention, film (a) is that the high-index material of 0.01-0.65 is made by the specific refractory power in the 380-780 nanometer wavelength range for the 1.8-2.6 Bees Wax.Beyond the 380-780 nano-area and in the wavelength region may near its border, the specific refractory power of described film (a) or optical extinction coefficient are not necessarily in above-mentioned scope, but preferably mainly in this scope.
Described specific refractory power is preferably 2.0-2.4.At this moment, specific refractory power is represented the numerical value by spectroscopic ellipsometry method of masurement mensuration.In the present invention, unless otherwise indicated, specific refractory power is represented the numerical value measured by this method.
In addition, the optical extinction coefficient of above-mentioned high-index material is 0.01-0.65.This optical extinction coefficient is preferably 0.05-0.5.Herein, optical extinction coefficient is represented the numerical value by spectroscopic ellipsometry method of masurement mensuration.In the present invention, unless otherwise indicated, optical extinction coefficient is always represented the numerical value by this kind method mensuration.
The geometrical film thickness degree of the film of being made by this high-index material (a) is preferably the 2-80 nanometer.Preferred film thickness is according to the changes in material of the lamination that constitutes film (a) or antireflective coating, but described film thickness is preferably the 5-70 nanometer, more preferably the 10-40 nanometer.As mentioned below, when antireflective coating of the present invention had a plurality of films (a), the film thickness of each film (a) was preferably within above-mentioned scope.
Herein, described geometrical film thickness kilsyth basalt shows the numerical value that records by profilograph.In the present invention, the film thickness of film is represented the geometrical film thickness degree.In addition, in the present invention, unless otherwise indicated, the geometrical film thickness degree is always represented the numerical value by this kind method mensuration.
In anti reflection glass of the present invention, this film (a) absorbs visible light, thereby can reduce the transmission of visible light to the indoor slightly, reduces the heat of direct sunlight.
In anti reflection glass of the present invention, described film (b) is 1.56 low-index material to the maximum by the specific refractory power in the 380-780 nanometer wavelength range and makes.Described specific refractory power preferably is 1.50 to the maximum, especially preferably is 1.48 to the maximum.Described film (b) preferably extinction ratio is the film of 0 substantially transparent substantially.
In anti reflection glass of the present invention, this film (b) can reduce reflectivity by the interference of light of above-mentioned film (a).
In addition, the geometrical film thickness degree of the film of being made by this kind low-index material (b) is preferably the 80-300 nanometer.Described film thickness is 100-200 more preferably, is preferably 120-160 especially.When film (b) had this kind thickness, its reflection preventing ability for the incident light that tilts obtained to improve.
Anti reflection glass of the present invention comprises therefore the incident light that tilts being had film (a) with above-mentioned thickness and character etc. and (b) etc. enough reflection preventing ability, and have high visible light transmissivity at least.
In described sheet glass with antireflective coating, with the reflectivity (R of 60 ° input angle incident visible lights on the film surface of antireflective coating
v) preferably be 12% to the maximum, especially preferably be 11% to the maximum.In addition, under 0 ° input angle condition, reflectivity preferably is 8.5% to the maximum, especially preferably is 6.5% to the maximum.Herein, visible reflectance (R
v) numerical value be the numerical value that comprises backside reflection under 60 ° of input angles and the 0 ° of input angle condition.
Herein, at 0 ° of input angle incident transmission of visible light (T
v) preferably be at least 77%, especially preferably be at least 82%.
The sheet glass with antireflective coating with this kind reflecting properties and transmission of visible light can be suitably as the sheet glass that is positioned at automobile inner side in the windshield.The windshield glass of automobile is normally by being provided with the middle layer that resin is made between the layer glass sheet, this layer glass sheet is the stacked and laminated glass that obtains.When using the sheet glass with antireflective coating of the present invention to make laminated glass, make when its surface with antireflective coating is positioned at automobile inner side, at 60 ° input angle incident visible lights at the lip-deep reflectivity (R of the film of described antireflective coating
v) can be up to 11%, when input angle was 0 °, this reflectivity was up to 8%.Visible reflectance (R
v) numerical value be the numerical value that comprises backside reflection under the situation of 60 ° of input angles and 0 ° of input angle.In addition, the transmission of visible light (T under 0 ° of input angle
v) can be at least 70%, this represents that described glass has enough low reflecting properties to oblique incidence light, also has high visible light transmissivity.
Herein, transmission of visible light (T of the present invention
v) and visible reflectance (R
v) be the numerical value that calculates according to JIS R3106.In addition, from the transmission of visible light (T of surperficial incident light with antireflective coating
v) be identical with the transmission of visible light of the surperficial incident light of antireflective coating never.
The material that constitutes film (a) and film (b) is described below.Described film (a) and film (b) can be made by each free various material, as long as described material has above-mentioned specific refractory power and optical extinction coefficient, and the sheet resistance that comprises the antireflective coating of film (a) and film (b) is at least 1k Ω/ and gets final product.
In the present invention, the main ingredient of the high-index material of formation film (a) preferably comprises the metal oxide (A) that is selected from following at least a element: Co, Al, Sn, Zn, Zr and V.
Described metal oxide (A) can comprise for example Co-Al oxide compound, Co-Zn-Al oxide compound, Co-Al-Si oxide compound, Co-Zn-Si oxide compound, Co-Si oxide compound or Zr-Si-V oxide compound.Described metal oxide (A) can be the mixture of many different sorts materials.
Herein for example " Co-Al oxide compound " expression " material of forming by one or more cobalt atoms, one or more aluminium atom and one or more Sauerstoffatom ".In the present invention, " material of being made up of one or more cobalt atoms, one or more aluminium atom and one or more Sauerstoffatom " is not limited to composite oxides, but comprise various oxide compounds, wherein forming various combinations between a kind of atoms metal and another atoms metal or between atoms metal and Sauerstoffatom, perhaps can be many kinds of hopcalites.In addition, it can be composite oxides and various hopcalite.This is because according to type or film forming method, and metal oxide comprises metal oxide that independent compound (oxide compound) is formed and the mixture of being made up of multiple compound.
In this specification sheets, be that example makes an explanation with " Co-Al oxide compound ", but identical definition also is applied to other oxide compound, for example Co-Zr-Al oxide compound, Co-Al-Si oxide compound, Co-Zn-Si oxide compound, Co-Si oxide compound or Zr-Si-V oxide compound.
Specifically, " Co-Al oxide compound " comprises CoAl
xO
y(0.5≤X≤15,1.75≤Y≤24) and CoO
z(1≤Z≤1.5) and Al
2O
3Mixture.In addition, " Co-Zn-Si oxide compound " comprise (Co, Zn)
2SiO
4In addition, " Co-Si oxide compound " comprises Co
2SiO
4In addition, " Zr-Si-V oxide compound " comprises the adulterated ZrSiO of V-
4
Described metal oxide (A) preferably is selected from following a kind of: Co-Al oxide compound, Co-Zn-Al oxide compound and Co-Al-Si oxide compound, more preferably Co-Al oxide compound.
In addition, described metal oxide (A) preferably comprises Co and Al, and the atomic ratio of Al and Co (Al/Co) is 0.5-15.This ratio (Al/Cl) is 1-7, more preferably 1.4-3 more preferably.
In addition, described metal oxide (A) preferably is selected from following at least a: the Co-Al oxide compound, and Co-Zn-Al oxide compound and Co-Al-Si oxide compound, and have above-mentioned Al/Co ratio.
This be because when described metal oxide (A) be mentioned kind, and when having the oxide compound of above-mentioned Al/Co ratio, for 0 ° of incident visible light, use the transmission variable color rate of the laminated glass of described metal oxide (A) to be 0.02 to the maximum, reflection variable color rate is 0.05 to the maximum.
Herein, in the present invention, described transmission variable color rate and reflection variable color rate are represented poor (the Δ x of following two kinds of tones separately, Δ y) absolute value: use illuminant-C according to JIS-Z8722 as the color measuring light source, in the x-y system of coordinates, map, to the tone that uses the laminated glass with sheet glass of antireflective coating of the present invention to record; And in the x-y system of coordinates, map in an identical manner, to the tone of the laminated glass of using glass baseplate (not forming the glass baseplate of antireflective coating on it).
Described film (a) preferably comprises above-mentioned metal oxide (A) as main ingredient, and described " main ingredient " expression content is at least the component of 90 quality %.That is to say, be benchmark in the total mass of the high-index material that constitutes film (a), and the content of described metal oxide (A) preferably is at least 90 quality %.This content preferably is at least 95 quality %, more preferably is at least 98 quality %, 100 quality % more preferably, and it does not contain other component substantially.This is because when content is very high, obtains having the suitable specific refractory power and the high-index material of optical extinction coefficient easily.
The material that constitutes high-index material except that metal oxide (A) is had no particular limits.These materials can be any materials, as long as the specific refractory power of the whole high-index material of being made up of metal oxide (A) and other material and optical extinction coefficient are in above-mentioned pre-determined range, as long as when about 560-700 ℃ pyroprocessing, described film can not form crackle because of changes in crystal structure or contraction and get final product.
The low refractive material that constitutes film (b) can be various materials, as long as the specific refractory power of described material mostly is 1.56 most.In the present invention, described material silicon oxide preferably.This is because silicon oxide has height endurability (wear resistance), can obtain being equal to or less than 5% turbidity value (haze value).
In the present invention, turbidity value is represented the numerical value that the method according to JIS K7105 and JIS K7136 records.
In addition, the content of silicon oxide is at least 90 quality % in the described low-index material, preferably is at least 95 quality %, more preferably 100 quality % (not containing other component substantially).This is that it can be reduced to turbidity value the highest by 5% (preferably the highest by 3%, more preferably the highest by 1%), and has low-refraction because this material has height endurability (wear resistance).In addition, in silicon oxide, preferred SiO
2This is because SiO
2Has low-refraction (about 1.45-1.48) at the wavelength place of 550 nanometers.When described low-index material mainly by SiO
2When forming, turbidity value can be up to 0.6%, and this is preferred.
Anti reflection glass of the present invention has the antireflective coating that is formed on the sheet glass, and described antireflective coating is made of at least two layers.Described " at least two layers " comprises film (a) and film (b) at least, and described film (b) is arranged on the outermost surface of antireflective coating.About the relation of the position between film (a) and the film (b), film (a) is arranged on a side of more close sheet glass, and film (b) is arranged on the side (outermost surface) away from sheet glass.In the present invention, as long as keep this position between film (a) and the film (b) to concern, can use any one antireflective coating in the various laminated.
Described antireflective coating can be the antireflective coating with two layers being made up of film (a) and film (b), described film (a) is arranged on the surface of sheet glass, film (b) is arranged on the film (a), and perhaps described antireflective coating can be except described film (a) and also comprise the stacked film of other film (b).
Described film (c) that is to say that the sheet glass with antireflective coating of the present invention also can comprise other film (film (c) hereinafter referred to as) except film (a) and film (b), as long as can not influence Electromgnetically-transparent, transmission of visible light (T
v) and visible reflectance (R
v) get final product.
The material that constitutes film (c) can be for example titanium oxide, zirconium white, titanium oxynitrides, niobium oxides, stannic oxide, silicon nitride, zirconium nitride, aluminium nitride or nitrogen stannic oxide.Described material can be many different types of mixtures, for example is at least two kinds mixture in these materials.The film that described film (c) is preferably made by titanium oxide or zirconium white.
In addition, the film thickness of film (c) depends on the mould material that constitutes antireflective coating or the order of these films, considers reflection preventing ability or accessibility (this will describe among the embodiment hereinafter in more detail) in the production, and this thickness is generally the 1-80 nanometer.Even in such scope, described lamination needs only it and has effect of the present invention also within the scope of the invention.
Embodiment
Below in conjunction with specific embodiment the present invention is described.In following examples (embodiment [1] is to [4]), glass baseplate is expressed as G, make " a " by film (a) note that high-index material is made, make " b " by film (b) note that low-index material is made, another film (film (c)) note is made " c ", represents with subscript from the stacked order of sheet glass.
[1]G/a
1/b
2
[2]G/a
1/c
2/a
3/b
4
[3]G/a
1/c
2/b
3
[4]G/c
1/a
2/b
3
Film (c) can be arranged between film (a) and the film (b) as described in enforcement mode [3], perhaps can be arranged between sheet glass and the film (a) as described in enforcement mode [4].In addition, when using film (c), can form two membranes (a) as described in the enforcement mode [2], film (c) can be positioned between film (a) and another tunic (a).
The quantity of film in the antireflective coating (a) can be single or multiple.Under a plurality of situations, the quantity of film (a) is two-layer.The quantity of film (b) is preferably 1, and the quantity of film (c) is preferably 1.
Herein, when at least two identical layers are provided as described in enforcement mode [2] (, providing two membranes (a)) for embodiment [2], these films (a
1And a
3) can be identical or different on thickness or material.
In antireflective coating of the present invention, the sum that constitutes the film of at least two layers is preferably 2-4, is preferably 2 or 3 especially.In the present invention, film (a) and film (c) are films, so their easy formation.Therefore, even the ading up in three layers or four layers the stacked of film that constitutes antireflective coating, this is stacked also can to provide the antireflective coating that has splendid throughput, can make with low cost.
To be that 1.6 film (a) specifically describes embodiment [1] as an example to [4] below with the atomic ratio (Al/Co) of Al and Co.When the atomic ratio (Al/Co) of Al and Co was other numerical value, the thickness of film can change according to atomic ratio.
Embodiment [1] can be following embodiment [1-1], wherein on glass baseplate, provides the film (a that is made by the Co-Al oxide compound according to following order
1) and by SiO
2Film (the b that makes
2).
[1-1] G/Co-Al oxide compound (a
1)/SiO
2(b
2)
In embodiment [1-1], film (a
1) film thickness be the 5-50 nanometer, be preferably the 10-40 nanometer, more preferably the 13-30 nanometer.
In addition, film (b
2) film thickness be the 105-170 nanometer, be preferably the 115-150 nanometer, more preferably the 120-145 nanometer.
In addition, only embodiment is film (a in the embodiment [1-1]
1) film thickness be the 13-30 nanometer, film (b
2) film thickness be the 120-145 nanometer.
As implement as described in the mode [2], preferred following embodiment [2-1] wherein forms four films altogether according to following order on sheet glass: by the film (a of Co-Al oxide compound preparation
1), by TiO
2Film (the c of preparation
2), another is by the film (a of Co-Al oxide compound preparation
3), by SiO
2Film (the b of preparation
4), the film thickness of these films is as follows.
[2-1] G/Co-Al oxide compound (a
1)/TiO
2(c
2)/Co-Al oxide compound (a
3)/SiO
2(b
4)
In embodiment [2-1], film (a
1) film thickness be the 2-30 nanometer, preferred 2-12 nanometer.
In addition, film (c
2) film thickness be the 2-22 nanometer, be preferably the 2-12 nanometer.
In addition, film (a
3) film thickness be preferably the 2-30 nanometer, 2-12 nanometer more preferably.
In addition, film (b
4) film thickness be preferably the 107-170 nanometer, 130-155 nanometer more preferably.
In addition, only embodiment is film (a in the embodiment [2-1]
1) film thickness be the 2-12 nanometer, film (c
2) film thickness be the 2-12 nanometer, film (a
3) film thickness be the 2-12 nanometer, film (b
4) film thickness be the 130-155 nanometer.
As implement as described in the mode [2], following embodiment [2-2] also is preferred, wherein forms four tunics altogether according to following order on sheet glass: the film (a that is made by the Co-Al oxide compound
1), by ZrO
2Film (the c that makes
2), another film (a that makes by the Co-Al oxide compound
3), and by SiO
2Film (the b that makes
4), the film thickness of these films is as follows.
[2-2] G/Co-Al oxide compound (a
1)/ZrO
2(c
2)/Co-Al oxide compound (a
3)/SiO
2(b
4)
In embodiment [2-2], film (a
1) film thickness be the 2-30 nanometer, be preferably the 2-12 nanometer.
In addition, film (c
2) film thickness be the 2-50 nanometer, be preferably the 2-37 nanometer.
In addition, described film (a
3) film thickness be the 2-30 nanometer, 2-12 nanometer more preferably.
In addition, described film (b
4) film thickness be preferably the 87-170 nanometer, 115-155 nanometer more preferably.
In addition, only embodiment is film (a in the embodiment [2-2]
1) film thickness be the 2-12 micron, film (c
2) film thickness be the 2-37 nanometer, film (a
3) film thickness be the 2-12 nanometer, film (b
4) film thickness be the 115-155 nanometer.
For embodiment [3], following embodiment [3-1] is preferred, wherein according to following order, forms trilamellar membrane altogether on sheet glass: the film (a that is made by the Co-Al oxide compound
1), by TiO
2Film (the c that makes
2), and by SiO
2Film (the b that makes
3), the film thickness of these films is as described below.
[3-1]G/Co-Al(a
1)/TiO
2(c
2)/SiO
2(b
3)
In embodiment [3-1], film (a
1) film thickness be the 2-30 nanometer, be preferably the 7-17 nanometer.
In addition, film (c
2) film thickness be the 2-25 nanometer, preferred 2-15 nanometer.
In addition, film (b
3) film thickness be the 107-170 nanometer, 122-155 nanometer more preferably.
In addition, the only embodiment of embodiment [3-1] is film (a
1) film thickness be the 7-17 nanometer, film (c
2) film thickness be the 2-15 nanometer, film (b
3) film thickness be the 122-155 nanometer.
As embodiment [3], also preferred following embodiment [3-2] wherein forms trilamellar membrane according to following order: the film (a that the Co-Al oxide compound is made altogether on sheet glass
1), ZrO
2Film (the c that makes
2), and SiO
2Film (the b that makes
3), the film thickness of these films is as follows.
[3-2] G/Co-Al oxide compound (a
1)/ZrO
2(c
2)/SiO
2(b
3)
In embodiment [3-2], film (a
1) film thickness be the 2-32 nanometer, be preferably the 4-17 nanometer.
In addition, film (c
2) film thickness be the 2-50 nanometer, be preferably the 5-50 nanometer.
In addition, film (b
3) film thickness be the 85-170 nanometer, 85-155 nanometer more preferably.
In addition, only embodiment is film (a in the embodiment [3-2]
1) film thickness be the 4-17 nanometer, film (c
2) film thickness be the 5-50 nanometer, film (b
3) film thickness be the 85-155 nanometer.
As embodiment [4], following embodiment [4-1] is preferred, wherein forms trilamellar membrane altogether according to following order on sheet glass: by TiO
2Film (the c that makes
1), the film (a that makes by the Co-Al oxide compound
2), by SiO
2Film (the b that makes
3), the film thickness of these films is as follows.
[4-1] G/TiO
2(c
1)/Co-Al oxide compound (a
2)/SiO
2(b
3)
In embodiment [4-1], film (c
1) film thickness be the 2-17 nanometer, be preferably the 5-10 nanometer.
In addition, film (a
2) film thickness be preferably the 2-32 nanometer, 9-15 nanometer more preferably.
In addition, film (b
3) film thickness be preferably the 107-170 nanometer, 130-155 nanometer more preferably.
In addition, only embodiment is film (c in the embodiment [4-1]
1) film thickness be the 5-10 nanometer, film (a
2) film thickness be the 9-15 nanometer, film (b
3) film thickness be the 130-155 nanometer.
For embodiment [4], also preferred following embodiment [4-2] wherein forms three layers according to following order: altogether by ZrO on sheet glass
2Film (the c that makes
1), the film (a that makes by the Co-Al oxide compound
2), by SiO
2Film (the b that makes
3), the film thickness of these films is as follows.
[4-2] G/ZrO
2(c
1)/Co-Al oxide compound (a
2)/SiO
2(b
3)
In embodiment [4-2], film (c
1) film thickness be 2-50nm, be preferably 5-50nm, more preferably 5-30nm.
In addition, film (a
2) film thickness be 2-32nm, be preferably 7-22nm, more preferably 7-17nm.
In addition, film (b
3) film thickness be 85-170nm, be preferably 107-158nm.
In addition, only embodiment is film (c in the embodiment [4-2]
1) thickness be the 5-30 nanometer, film (a
2) film thickness be 7-17nm, film (b
3) film thickness be 107-158nm.
In addition, at above-mentioned embodiment [1] in [4], clear soda-lime glass that sheet glass (G) is preferably colourless or green type colored transparent glass with UV-break-in facility.
In addition, anti reflection glass of the present invention has enough wear resistancies, and to electromagnetic transmissivity, its structure can be simple structure, wherein film (a) and film (b) are provided on the sheet glass, make described anti reflection glass have splendid throughput, and can be with the low cost manufacturing.In addition,, reduced material cost, made and to make described glass with low cost because the thickness of whole antireflective coating can be very thin.
In addition, in anti reflection glass of the present invention, because each material that freely has following character of film (a) and film (b) is made: even be subjected to heat treated the time at film, the form of this material can not change (in other words yet, after the thermal treatment, there is no different before the character of film and the thermal treatment), so the thermal treatment (when carrying out BENDING PROCESS or drawing process) that described film carries out when making has enough tolerances, technology after can finishing.For example, in the manufacturing processed of windshield, under about 560-700 ℃ high temperature the flat glass that has formed film on it is carried out bending process, the sheet glass with antireflective coating of the present invention has tolerance to this technology.That is to say that even at high temperature carry out BENDING PROCESS, the following problem that influences effect of the present invention can not take place still, for example: form crackle on film, perhaps film character changes.Therefore, the sheet glass with antireflective coating of the present invention is suitable as the glass that is positioned at the car inboard in the windshield.In addition, even the sheet glass with antireflective coating of the present invention in drawing process, is subjected to thermal treatment under about 560-700 ℃ temperature, the following problem that influences effect of the present invention still can not take place, for example: form crackle on film, perhaps film character changes.Therefore, described sheet glass is suitable as the tempered window glass, for example as the glider glass window of automobile.
In addition, antireflective coating of the present invention does not also show enough reflection preventing ability under it is subjected to the situation of high-temperature heat treatment of BENDING PROCESS or drawing process.That is to say that the sheet glass with antireflective coating of Zhi Zaoing also shows above-mentioned visible light transmission (T in the following manner
v) and visible light reflectivity (R
v): with predetermined shape cambering glass sheets, sheet glass is carried out tempering, on the surface of described sheet glass, form antireflective coating of the present invention then, thereby described sheet glass with antireflective coating can be used to prevent reflection effectively, but also has splendid wear resistance and to electromagnetic transmissivity.
Anti reflection glass of the present invention is preferred for laminated glass.This laminated glass is also included within the scope of the present invention.This laminated glass specifically is called " laminated glass of the present invention ".
That is to say, laminated glass of the present invention is the laminated glass that is used for window, it comprises first sheet glass, second sheet glass with antireflective coating, and be arranged on middle layer between described first sheet glass and second sheet glass, described second sheet glass is arranged on the indoor, and described second sheet glass with antireflective coating is the sheet glass with antireflective coating of the present invention.In laminated glass of the present invention, the outermost surface of described antireflective coating is an indoor side surface.
This laminated glass of the present invention is preferably used as for example windshield glass of automobile.When laminated glass of the present invention is used for this application, might suppresses to form projection, thereby improve officer's the visual field from the light of dashboard.
Herein, described first sheet glass and second sheet glass can be separately with the sheet glass that can be used in the invention described above sheet glass identical aspect (for example) material and the thickness.For example, described first sheet glass and second sheet glass thickness separately can be the 1.5-3.0 millimeter.In the case, described first sheet glass can have identical thickness with second sheet glass, perhaps can have different thickness.When laminated glass of the present invention is used for automobile window, for example, described first sheet glass and second sheet glass can each self-forming 2.0 millimeters thickness, perhaps they can each self-forming 2.1 millimeters thickness.In addition, when laminated glass of the present invention is used for automobile window, for example, second sheet glass can form the thickness less than 2 millimeters, first sheet glass can form the thickness greater than 2 millimeters, make that the total thickness of the laminated glass be used for window is very little, described glass can tolerate the applied external force from vehicle outer side.Described first sheet glass and second sheet glass can have smooth shape or crooked shape separately.In many cases, vehicle, particularly vehicle window has curved part, and therefore in many cases, the shape of first sheet glass and second sheet glass is crooked.
In addition, described middle layer can be a layer arbitrarily, as long as it can be used in laminated glass.For example, it can be polyvinyl butyral acetal (PVB) or vinyl-vinyl acetate copolymer (EVA), wherein preferred PVB.The thickness in middle layer is about 0.76 millimeter polyvinyl butyral acetal for for example 0.3-0.8mm, preferred thickness.In addition, these middle layers can be the middle layers that infrared shielding particle (for example ITO (tin indium oxide)) wherein is set.
The Co-Al oxide compound that is used for above-mentioned embodiment more preferably Al/Co than being 1-7.This is because use this material to constitute, and the visible transmission variable color rate of 0 ° of input angle and reflection variable color rate are respectively the highest 0.01 and the highest by 0.05.
In the laminated glass that is used for window of the present invention, at the reflectivity (R of 60 ° of input angle incident visible lights on the film surface
v) preferably be up to 11%, especially preferably be up to 10%.In addition, under 0 ° of input angle condition, reflectivity is up to 8%, especially preferably is up to 6%.In addition, visible reflectance (R
v) numerical value be the numerical value of backside reflection under 60 ° of input angles and 0 ° of input angle condition.
In addition, the transmission of visible light (T under 0 ° of input angle condition
v) preferably be at least 70%, especially preferably be at least 75%.As transmission of visible light (T
v) very high the time, reflection preventing ability can reduce, therefore, transmission of visible light is preferably the highest to be about 85%.
The laminated glass reflectivity (comprising backside reflection) to visible light under 60 ° of input angle conditions that has the antireflective coating of above-mentioned embodiment [1] to [4] and have a said structure is 11%, and the transmission of visible light under 0 ° of input angle condition is at least 70%.In addition, described laminated glass can be equal to or less than 8% to the reflectivity (comprising backside reflection) of the visible light of 0 ° of input angle.Therefore, laminated glass of the present invention can be especially suitable for use as the windshield glass of automobile.
In addition, in the respective embodiments described above [1]-[4], particularly preferred embodiment is shown as " only embodiment ".When the anti reflection glass manufacturing of using only embodiment has the laminated glass of said structure, laminated glass of the present invention is up to 10% to the reflectivity (comprising backside reflection) with 60 ° of input angle incident visible lights, and the transmission of visible light under 0 ° of input angle condition is at least 75%.
Herein, in the present invention, the visible reflectance of 60 ° of input angles, the visible reflectance of 0 ° of input angle, and the transmission of visible light of 0 ° of input angle is to use the A light sources according to JIS-R 3106, and the numerical value that light is recorded from film surface incident.
Next described and made the have sheet glass of antireflective coating and the manufacturing process of laminated glass of the present invention of the present invention.
The method that is used for forming film (a), film (b) and (depending on the circumstances or the needs of the situation) film (c) is not particularly limited, but can use for example conventional known method.For example can adopt the CVD method, sputtering method or thermal decomposition method.Wherein, these films preferably form by sputtering method.
For sputtering method, can comprise for example DC (direct current) sputtering method, AC (interchange) sputtering method, high-frequency sputtering or magnetron sputtering method.Wherein preferred DC magnetron sputtering method or AC magnetron sputtering method.This is because these methods have splendid technology stability, therefore is easy to the big area film forming.
For example, form in the film of being made by the Co-Al oxide compound (a) on sheet glass, use two targets, Co target and Al target use the gas that contains Sauerstoffatom to carry out reactive sputtering as sputter gas, thereby can form film (a) on sheet glass.Herein, by Change Example as putting on the voltage of two targets, can change the Co that comprises in the film (a) that is formed on the glass baseplate paper and the ratio of Al.In addition, in this sputtering method, can use the target that comprises Co and Al.
In addition, also can use the target that comprises Co, Al and O.In addition, also can be with oxygen-free gas as sputter gas.In addition, in the film (a) that forms the Co-Zn-Al oxide compound, can use three targets, perhaps can use a target that comprises these three kinds of elements.
The method that forms silicon oxide film (b) on the surface that is formed at the film (a) on the glass sheet surface is not particularly limited.For example can comprise and use silicon carbide (SiC) to contain the reactive sputtering of the gas of Sauerstoffatom as sputter gas as target, use.
In addition, in the film (c) that forms titanium oxide, the method that can mention is to use TiO
x(1＜X＜2) carry out reactive sputtering as the gas that target, use contain Sauerstoffatom as sputter gas.
In addition, when forming zirconic film (c), for example, the method that can mention is to use zirconium to carry out reactive sputtering as the gas that target, use contain Sauerstoffatom as sputter gas.
In this sputtering method, the rare gas element of carbonic acid gas or argon gas and so on can be used in combination with this sputter gas.
Sputtering condition can be according to suitably decisions such as the kind of the film that forms, thickness.In addition, the total pressure of sputter gas can be a pressure arbitrarily, as long as this pressure can carry out stable glow discharge.
Laminated glass of the present invention can make by for example following steps.At first, the sheet glass with antireflective coating to the invention described above carries out bending.Then, after described sheet glass with antireflective coating is carried out bending step, stacked middle layer and another sheet glass (sheet glass that does not have antireflective coating, described middle layer and another sheet glass are with described sheet glass bending with antireflective coating, make their curvature equate), thereby the surface of described antireflective coating is arranged on automobile inner side, under vacuum pressure, they is heated and the pressure combination.
Embodiment
[1] specific refractory power of film (a) and the evaluation of optical extinction coefficient
Al target and Co target are arranged on the negative electrode in the vacuum chamber as sputtering target.In addition, described vacuum chamber is pumped to 1.3 * 10
-3Handkerchief or lower, sputter gas (Ar and the O that argon gas and oxygen are formed then
2Mixed gas) charge into described vacuum chamber, make that pressure is 4.0 * 10
-1Handkerchief.Use the DC pulse power then, use Al target and Co target to carry out reactive sputtering simultaneously, (Corning Incorporated (Corning) makes sheet glass in being arranged at described vacuum chamber, product type: 1739) form the film of being made by the oxide compound that comprises Al and Co (a) on the surface.In following examples, described film (a) also can be described as CoAl
xO
yFilm.
Then in the small size band oven, to the CoAl that has that makes
xO
yThe sheet glass of film is heat-treated.Heat-treat condition is as follows: design temperature is 650 ℃, and heat treatment time is 15 minutes.After thermal treatment, use XPS (the sub-spectrum of X-ray photoelectric) to measure CoAl then
xO
yAtomic ratio in the film between Co atom and the Al atom.
Table 1 has shown that filming condition is (to the power that each target applies, Ar/O
2Volume ratio) and the atomic ratio measuring result.
Table 1
| Al power (watt) | Co power (watt) | Ar/O 2Gas flow rate (sccm) | The Al/Co atomic ratio | |
| Sample 1 | 700 | 50 | 21/9 | 20.2/1 |
| Sample 2 | 700 | 100 | 21/9 | 5.6/1 |
| Sample 3 | 700 | 200 | 19/11 | 2.4/1 |
| Sample 4 | 700 | 300 | 18/12 | 1.6/1 |
| Sample 5 | 700 | 400 | 18/12 | 1.1/1 |
In addition, use oval spectrum polarimeter to measure thermal treatment CoAl afterwards
xO
yThe specific refractory power of film in the 380-780 nanometer wavelength range and the wavelength dispersion of optical extinction coefficient.Fig. 1 and Fig. 2 have shown measuring result.Sample 1 does not show specified specific refractory power of the present invention and optical extinction coefficient numerical value, and this is because the al atomic ratio example is too high.
[2] specific refractory power of film (b) and the evaluation of optical extinction coefficient
The Si target is set as sputtering target on the negative electrode in vacuum chamber.Then, described vacuum chamber is pumped to 1.3 * 10
-3Handkerchief or lower, the sputter gas (Ar/O that argon gas and oxygen are formed then
2=18/12 (volume ratio)) introduce described vacuum chamber, make that pressure is 4.0 * 10
-1Handkerchief.Then, use the DC pulse power, carry out the sputter of Si target response, form by SiO on the silicon wafer surface in being arranged at vacuum chamber
2The film of making (b).This film (b) is also referred to as SiO hereinafter
2Film.Table 2 has shown filming condition.
Table 2
| Si power | Ar/O 2Gas flow rate (sccm) |
| 500W | 18/12 |
What make then, has a SiO
2The silicon wafer of film is heat-treated in the small size band oven.Heat-treat condition is as follows: design temperature is 650 ℃, and heat treatment time is 15 minutes.Use oval spectrum polarimeter in the 380-780 nanometer wavelength range, to measure thermal treatment SiO afterwards then
2The specific refractory power of film and the wavelength dispersion of optical extinction coefficient.
As a result, the optical extinction coefficient in the 380-780 nanometer range is 0.Fig. 3 has shown SiO
2The wavelength dispersion of the specific refractory power of film.
[3] has the preparation of the sheet glass of antireflective coating
With water white transparency soda-lime glass ((the Asahi Glass Company of Asahi Glass Co., Ltd, Limited) make, thickness: 2.3mm, hereinafter referred to as " FL ") as sheet glass, on described sheet glass, form each the stacked antireflective coating of the embodiment 1-4 shown in the table 3, make sheet glass with antireflective coating.
In each embodiment 1 and 2, under the filming condition suitable, on the surface of FL, form CoAl herein, with the sample 4 of top [1]
xO
yFilm.In addition, under the filming condition suitable, on the top of this film, form SiO with top [2]
2Film.
In addition, in each embodiment 3 and 4, under the filming condition suitable, on the surface of FL, form CoAl with the sample 2 of top [1]
xO
yFilm.Under the filming condition suitable, on the top of this film, form SiO with top [2]
2Film.
Table 3 has shown the thickness of each embodiment 1-4.In addition, table 3 has also shown each CoAl that use XPS (the sub-spectrum of X-ray photoelectric) measures
xO
yAtomic ratio in the film between Co atom and the Al atom.In addition, table 4 has shown visible reflectance and the transmission of visible light that has the sheet glass of antireflective coating among each the embodiment 1-4 that obtains by simulation.
Table 3
| Membrane structure | The Al/Co atomic ratio | |
| Embodiment 1 | FL (2.3 millimeters)/CoAl xO y(16 nanometer)/SiO 2(153 nanometer) | 1.6∶1 |
| Embodiment 2 | FL (2.3 millimeters)/CoAl xO y(14 nanometer)/SiO 2(143 nanometer) | 1.6∶1 |
| Embodiment 3 | FL (2.3 millimeters)/CoAl xO y(20 nanometer)/SiO 2(125 nanometer) | 5.6∶1 |
| Embodiment 4 | FL (2.3 millimeters)/CoAl xO y(20 nanometer)/SiO 2(140 nanometer) | 5.6∶1 |
Table 4
| Transmission of visible light | Visible reflectance (60 ° of input angles) (%) | Visible reflectance (0 ° of input angle) (%) | |
| Embodiment 1 | 81.3 | 10.3 | 6.8 |
| Embodiment 2 | 84.3 | 10.6 | 5.2 |
| Embodiment 3 | 89.1 | 12.1 | 4.1 |
| Embodiment 4 | 88.3 | 11.2 | 5.0 |
[4] preparation of laminated glass and evaluation
The sheet glass with antireflective coating of each the embodiment 1-4 that makes in above-mentioned [3] is 600 ℃ of following thermal treatments 8 minutes, then in indoor cooling gradually.Then, each sheet glass after the thermal treatment and middle layer (0.76 millimeter) and green transparent soda-lime glass ((the Asahi Glass Company of Asahi Glass Co., Ltd that polyvinyl butyral acetal makes with antireflective coating, Limited) make, thickness: 2.3 millimeters, hereinafter referred to as " VLF ") stacked, make the surface of antireflective coating become the indoor, use the sheet glass of embodiment 1-4 to make four kinds of laminated glass respectively with antireflective coating.Then, for each laminated glass, with spectrophotometer (the U4100, (Hitachi of Hitachi Ltd, Ltd.) make) measure it to optical transmission rate and reflectivity in the 380-780 nanometer wavelength range, obtain visible transmission T from VFL sheet glass side incident light
v(%), and at the visible reflectance R of film (b) side with 60 ° of input angles and 0 ° of input angle incident light
v(%).In addition, by using 2-pin probe resistance rate meter (Hiresta IP, Mitsubishi's petrochemical industry (Mitsubishi Petrochemical) is made), four kinds of laminated glass antireflective coating is separately measured sheet resistance.
As a result, as shown in table 5, the resistivity of each laminated glass is at least 1G Ω/.In addition, the transmission of visible light of each laminated glass under 0 ° of input angle condition is at least 70%, is up to 11% at the visible reflectance of 60 ° of input angles, and the visible reflectance under 0 ° of input angle condition is up to 8%.
Table 5
| Transmission of visible light (0 ° of input angle) (%) | Visible reflectance (60 ° of input angles) (%) | Visible reflectance (0 ° of input angle) (%) | Resistivity (Ω/) | |
| Embodiment 1 | 74.4 | 9.6 | 6.9 | 3.3×10 9 |
| Embodiment 2 | 76.7 | 9.4 | 5.1 | 7.2×10 9 |
| Embodiment 3 | 81.2 | 10.6 | 3.8 | 7.8×10 12 |
| Embodiment 4 | 80.0 | 9.8 | 4.9 | 4.3×10 12 |
In addition, carry out after the above-mentioned thermal treatment each with observation by light microscope and have the antireflective coating surface of the sheet glass of antireflective coating, prove not form crackle.
[5] turbidity ratio is estimated
Make the sheet glass 5 with antireflective coating according to the mode identical with embodiment 2 in [3], difference is that the film thickness of film (a) and film (b) is as follows:
FL (2.3 millimeters)/CoAl
xO
y(16 nanometer)/SiO
2(140 nanometer)
Use turbidometer to have the turbidity value of the sheet glass 5 of antireflective coating at two point measurements, turbidity value is respectively 0.1% and 0.3%.
The full text that the Japanese patent application of submitting on February 21st, 2007 is 2007-040928 number comprises specification sheets, claims, accompanying drawing and summary, all is incorporated by reference into herein.
Claims (12)
1. sheet glass with antireflective coating, it comprises sheet glass and antireflective coating, described antireflective coating is made up of at least two layers, be provided on the surface of described sheet glass, described antireflective coating comprises film (a) and film (b), described film (a) is made by high-index material, the specific refractory power of described high-index material in the 380-780 nanometer wavelength range is 1.8-2.6, optical extinction coefficient is 0.01-0.65, described film (b) is made by low-index material, the specific refractory power of described low-index material in the 380-780 nanometer wavelength range is up to 1.56, described film (b) is positioned at the outermost surface of described antireflective coating, and the sheet resistance of described antireflective coating is at least 1k Ω/.
2. the sheet glass with antireflective coating as claimed in claim 1 is characterized in that, the geometrical film thickness degree of described film (a) is the 2-80 nanometer, and the geometrical film thickness degree of described film (b) is the 80-300 nanometer.
3. the sheet glass with antireflective coating as claimed in claim 1 is characterized in that, the main ingredient of described high-index material is metal oxide (A), it comprise be selected from following at least a: Co, Al, Si, Zn, Zr and V.
4. the sheet glass with antireflective coating as claimed in claim 3 is characterized in that, described metal oxide (A) be selected from following at least a: the Co-Al oxide compound, the Co-Zn-Al oxide compound, Co-Al-Si oxide compound, Co-Zn-Si oxide compound, Co-Si oxide compound and Zr-Si-V oxide compound.
5. the sheet glass with antireflective coating as claimed in claim 3 is characterized in that, described metal oxide (A) comprises Co and Al, and the atomic ratio of Al and Co (Al/Co) is 0.5-15.
6. the sheet glass with antireflective coating as claimed in claim 3 is characterized in that, described metal oxide (A) is CoAl
XO
Y(0.5≤X≤15,1.75≤Y≤24).
7. the sheet glass with antireflective coating as claimed in claim 1 is characterized in that described low-index material is a silicon-dioxide.
8. the laminated glass that is used for window, it comprises first sheet glass, second sheet glass with antireflective coating of forming by at least two layers, and the middle layer between described first sheet glass and second sheet glass, described second sheet glass is arranged on the indoor, described second sheet glass provides antireflective coating, and this second sheet glass is that the outermost surface of described antireflective coating is arranged on the indoor as each defined sheet glass with antireflective coating among the claim 1-7.
9. the laminated glass that is used for window as claimed in claim 8, its transmission of visible light (Tv) under 0 ° of input angle condition is at least 70%.
10. the laminated glass that is used for window as claimed in claim 8 is characterized in that, under 60 ° of input angle conditions, visible light is 11% to the maximum at the reflectivity (Rv) on the film surface of described antireflective coating.
11. the laminated glass that is used for window as claimed in claim 8 is characterized in that, under the condition of 0 ° of input angle, visible light is 8% to the maximum at the reflectivity (Rv) on the film surface of antireflective coating.
12. one kind prepares the method with sheet glass of antireflective coating as claimed in claim 1, it is characterized in that, described at least film (a) forms by sputter.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007040928A JP2008201633A (en) | 2007-02-21 | 2007-02-21 | Glass sheet with antireflection film and laminated glass for window |
| JP2007040928 | 2007-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101250028A true CN101250028A (en) | 2008-08-27 |
Family
ID=39431084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200810081054XA Pending CN101250028A (en) | 2007-02-21 | 2008-02-21 | Glass sheet with antireflection film and laminated glass for windows |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20080199671A1 (en) |
| EP (1) | EP1962109A3 (en) |
| JP (1) | JP2008201633A (en) |
| CN (1) | CN101250028A (en) |
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| CN102782528A (en) * | 2009-12-11 | 2012-11-14 | 日本板硝子株式会社 | Cover glass for photoelectric converter and process for producing same |
| CN103073196A (en) * | 2013-02-08 | 2013-05-01 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass and laminated glass product thereof |
| CN103221847A (en) * | 2010-11-26 | 2013-07-24 | 法国圣戈班玻璃厂 | Transparent substrate comprising an anti-eflection coating |
| CN108312655A (en) * | 2017-01-16 | 2018-07-24 | 旭硝子株式会社 | Transparent base with antireflective coating |
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| JP5050063B2 (en) * | 2010-01-20 | 2012-10-17 | 株式会社東芝 | Solid-state imaging device |
| JP2011203345A (en) * | 2010-03-24 | 2011-10-13 | Panasonic Electric Works Co Ltd | Anti-reflection film and camera system |
| AT12888U1 (en) * | 2011-08-29 | 2013-01-15 | Eicon Gmbh | MULTILAYER XTRUDAT WITH ELASTOMERANTEIL |
| JP2015038978A (en) * | 2013-07-17 | 2015-02-26 | 日本電気硝子株式会社 | Wavelength conversion member |
| JP2017105643A (en) | 2014-04-24 | 2017-06-15 | 旭硝子株式会社 | Glass substrate with coating film and method for production thereof |
| WO2016066994A1 (en) * | 2014-10-31 | 2016-05-06 | Pilkington Group Limited | Anti-reflective coated glass article |
| US10377664B2 (en) * | 2014-11-12 | 2019-08-13 | Pilkington Group Limited | Coated glass article, display assembly made therewith and method of making a display assembly |
| CN105448200A (en) * | 2015-12-04 | 2016-03-30 | 中国电子科技集团公司第五十五研究所 | Method for improving OLED outdoor readability |
| US11021392B2 (en) | 2017-01-16 | 2021-06-01 | AGC Inc. | Transparent substrate with multilayer antireflective film containing an oxide of molybdenum |
| JP6864080B2 (en) * | 2017-03-30 | 2021-04-21 | 富士フイルム株式会社 | Laminates, building materials, window materials and radiative cooling equipment |
| CN110461786B (en) * | 2017-03-30 | 2022-12-09 | 旭硝子欧洲玻璃公司 | Glass for autonomous automobile |
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| KR20230021146A (en) | 2020-07-22 | 2023-02-13 | 에이지씨 가부시키가이샤 | Transparent substrate and image display device with antireflection film |
| JPWO2022181371A1 (en) | 2021-02-26 | 2022-09-01 | ||
| US20230229037A1 (en) | 2022-01-19 | 2023-07-20 | AGC Inc. | Anti-reflective film-attached transparent substrate and image display device |
| CN115593047B (en) * | 2022-09-29 | 2024-01-23 | 福耀玻璃工业集团股份有限公司 | Window glass and vehicle |
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|---|---|---|---|---|
| JPH1173119A (en) * | 1997-03-24 | 1999-03-16 | Konica Corp | Antireflection coat having electromagnetic wave shield effect and optical member having antireflection coat |
| US6436541B1 (en) * | 1998-04-07 | 2002-08-20 | Ppg Industries Ohio, Inc. | Conductive antireflective coatings and methods of producing same |
| JP2000047007A (en) * | 1998-07-31 | 2000-02-18 | Sony Corp | Antireflection film and cathode-ray tube |
| US6572990B1 (en) * | 1998-11-30 | 2003-06-03 | Asahi Glass Company, Limited | Transportation equipment window antireflection film, glass with antireflection film, laminated glass and production method therefor |
| WO2001024224A1 (en) * | 1999-09-30 | 2001-04-05 | Koninklijke Philips Electronics N.V. | Electric lamp |
| JP2003121603A (en) * | 2001-10-12 | 2003-04-23 | Bridgestone Corp | Antireflection film |
| KR100484102B1 (en) * | 2002-05-16 | 2005-04-18 | 삼성에스디아이 주식회사 | Composition for forming transparent conductive layer, transparent conductive layer formed therefrom and image display device employing the same |
| EP1845392A4 (en) * | 2005-01-31 | 2009-06-03 | Asahi Glass Co Ltd | Substrate with antireflection coating |
| JP4646730B2 (en) | 2005-08-05 | 2011-03-09 | 株式会社日立ハイテクノロジーズ | Surface foreign matter detection apparatus and detection method for plasma processing apparatus |
-
2007
- 2007-02-21 JP JP2007040928A patent/JP2008201633A/en not_active Withdrawn
-
2008
- 2008-02-12 EP EP08002552A patent/EP1962109A3/en not_active Withdrawn
- 2008-02-14 US US12/031,383 patent/US20080199671A1/en not_active Abandoned
- 2008-02-21 CN CNA200810081054XA patent/CN101250028A/en active Pending
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| CN102782528B (en) * | 2009-12-11 | 2015-02-25 | 日本板硝子株式会社 | Cover glass for photoelectric converter and process for producing same |
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| CN108312655A (en) * | 2017-01-16 | 2018-07-24 | 旭硝子株式会社 | Transparent base with antireflective coating |
| CN108312655B (en) * | 2017-01-16 | 2022-04-08 | Ａｇｃ株式会社 | Transparent substrate with antireflection film |
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| CN114734690B (en) * | 2017-01-16 | 2023-06-09 | Ａｇｃ株式会社 | Transparent substrate with antireflection film |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1962109A3 (en) | 2009-07-01 |
| US20080199671A1 (en) | 2008-08-21 |
| JP2008201633A (en) | 2008-09-04 |
| EP1962109A2 (en) | 2008-08-27 |
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Open date: 20080827 |